EP1771394B1 - Fiber optic moisture sensor - Google Patents

Fiber optic moisture sensor Download PDF

Info

Publication number
EP1771394B1
EP1771394B1 EP05765633A EP05765633A EP1771394B1 EP 1771394 B1 EP1771394 B1 EP 1771394B1 EP 05765633 A EP05765633 A EP 05765633A EP 05765633 A EP05765633 A EP 05765633A EP 1771394 B1 EP1771394 B1 EP 1771394B1
Authority
EP
European Patent Office
Prior art keywords
fiber optic
optic sensor
moisture
core
binding agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP05765633A
Other languages
German (de)
French (fr)
Other versions
EP1771394A2 (en
Inventor
Halime Usta Arcelik Anonim Sirketi YOGUN
Yavuz Arcelik Anonim Sirketi ERCIL
Yusuf Sabanci Universitesi MENCELOGLU
Naci Sabanci Universitesi Muhendislik ve INCI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arcelik AS
Original Assignee
Arcelik AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arcelik AS filed Critical Arcelik AS
Publication of EP1771394A2 publication Critical patent/EP1771394A2/en
Application granted granted Critical
Publication of EP1771394B1 publication Critical patent/EP1771394B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/105—Organic claddings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/12—General methods of coating; Devices therefor
    • C03C25/16—Dipping
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/66—Chemical treatment, e.g. leaching, acid or alkali treatment
    • C03C25/68—Chemical treatment, e.g. leaching, acid or alkali treatment by etching
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
    • G01N2021/7706—Reagent provision
    • G01N2021/7709—Distributed reagent, e.g. over length of guide
    • G01N2021/7716—Distributed reagent, e.g. over length of guide in cladding
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
    • G01N2021/7706—Reagent provision
    • G01N2021/7723—Swelling part, also for adsorption sensor, i.e. without chemical reaction
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
    • G01N2021/7706—Reagent provision
    • G01N2021/773—Porous polymer jacket; Polymer matrix with indicator
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/775—Indicator and selective membrane
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7776—Index
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/81—Indicating humidity
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02033—Core or cladding made from organic material, e.g. polymeric material

Definitions

  • This invention relates to a coating material that is applied on organic and/or inorganic surfaces and to a fiber optic sensor where this coating material is used.
  • Polyethylene Glycol (PEG) has a very high hydrophilic (likes water) property, detaining moisture. For this reason, its usage is well known especially for moisture sensor applications.
  • sensor material particularly Polyethylene Glycol (PEG) is to be coated on surfaces of glass or plastic fiber optic materials.
  • PEG material that is applied as moisture sensitive sensor material can not release the moisture content that it has detained at high moisture levels; thus, adversely affecting the repeatability and linearity of the data that the moisture sensor detects.
  • United States Patent US5109442 describes a fiber optic sensor structure which repels water from its surface and which includes long, hydrophobic (dislikes water) chained polymeric silanes.
  • Polymeric silanes have general structures where alkyltrialkoxysilanes or octadecyltrimethoxysilanes are used.
  • JP2003270141 discloses an optical fiber humidity sensor comprising a mixture formed of a hydrophilic material and a water-insoluble material as cladding layer.
  • the object of the present invention is to realize a fiber optic sensor according to the subject-matter of claim 1.
  • the fiber optic sensor is illustrated in the attached figures, where:
  • Fig. 1 - is a schematic view of a fiber optic sensor.Parts shown in figures are numbered as follows:
  • the fiber optic sensors (1) are particularly affected by moisture level deviations, and sense moisture levels.
  • Coating material that is the object of the present invention comprises a hydrophilic material that has a property to attract moisture that is applied on organic or inorganic surfaces and a hydrophobic material that avoids the detaining and releasing mechanisms of the moisture content with a hydrophilic material that attracts moisture and the accumulation of excessive moisture molecules inside the hydrophilic material, that simplifies and organizes the release of water molecules settled inside the hydrophilic material in the shortest time when moisture concentration decreases, and that has a property of repelling moisture.
  • hydrophilic material olygomer and/or polymer materials that are sensitive to various chemicals of hydroxyl, amino, thiol or carboxyl may be used.
  • polyethylene glycol (PEG) which has a property to detain moisture is utilized as a hydrophilic material.
  • hydrophobic material materials that comprise perfluoroalcohol (PFA) group which is known to have a hydrophobic and moisture repelling property are used.
  • PFA perfluoroalcohol
  • perfluoroalkyletylalcohol preferably perfluoroalkyletylalcohol is used as perfluoroalcohol.
  • the coating material comprises a binding agent that increases the grip of the hydrophilic and hydrophobic material to the surface to be coated.
  • the binding agent has an adhering effect and as a binding agent trialcoxy silane group preferably gamma - isocyanatopropyltriethoxysilane is applied.
  • hydrophilic material and binding agent mix that has an end group of trialcoxy silane is obtained.
  • the general formula of the hydrophilic material, the compound of PEG with trialcoxy silane coated end groups formed after the reaction of PEG and gamma - isocyanatopropyltriethoxysilan is as follows:
  • hydrophobic material When hydrophobic material is prepared, PFA and gamma - isocyanatopropyltriethoxysilane used as a binding agent are processed with the use of a solvent. The solution is mixed by the addition of a catalyst, tin (II) 2-ethylhexanoate, to the solution obtained at the end of this process.
  • a catalyst tin (II) 2-ethylhexanoate
  • Coating material is obtained by dissolving and/or dispersing the hydrophilic and hydrophobic material and binding agent mixture in water with certain proportions and different concentrations. For example:
  • PEG material with a hydroxyl end is dissolved in 180 ml toluene solvent.
  • This solution is processed with dean-stark distillation method for 3 hours and moisture content that is trapped inside the PEG material is removed from the material.
  • PEG and toluene solution, with the moisture removed from its content, is processed with 7.5 mmol gamma - isocyanatopropyltriethoxysilane for a certain period at approximately 50 °C; hence, the hydrophilic material and binding agent mixture is obtained.
  • PFA particularly 6 g perfluoroalkylethylalcohol, and 3.41 g gamma - isocyanatopropyltriethoxysilane that is used as a binding agent is dissolved in 42 ml tetrahydrofuran solvent.
  • Tin (II) 2-ethylhexanoate is included in this solution as a catalyst and the solution is mixed.
  • PFA reacts with one of the trialcoxy silane groups, gamma - isocyanatopropyltriethoxysilane, which is used as a binding agent and as a result of this reaction trialkoxy silane groups bind with urethane bonds to the ends of PFA chains.
  • hydrophobic material and binding agent By combining PFA and gamma - isocyanatopropyltriethoxysilane, a mixture of hydrophobic material and binding agent is obtained. Additionally, by combining the hydrophilic material, hydrophobic material and binding agent mixture, coating material is obtained.
  • Coating material can also be applied on silica glass material.
  • the fiber optic sensor (1) comprises a core (2) that is used as a light transmission line and that is preferably manufactured from plastic fiber optic material, a cladding (3) which thoroughly surrounds the core (2) and has a lower refractive index than the refractive index of the core (2) and is preferably manufactured from a plastic fiber optic material, a detector (4) manufactured from the coating material that is coated on organic or inorganic surfaces , a monochromatic transmitter (5) that is used as a light source and a receiver (6) that senses light.
  • a core (2) which is preferably manufactured from PMMA material is used.
  • the part of the cladding (3) which thoroughly surrounds the core (2) is partially or completely scratched just up to the surface of the core (2) with various methods; thus, the part that will be coated with the detector (4) is revealed.
  • the detector (4) manufactured from the coating material that includes hydrophilic and hydrophobic material is easily coated permanently to this part that is formed by scratching the cladding (3), creating a cross bond on PMMA material.
  • Detector (4) is coated preferably with dip coating method.
  • Light that is transmitted into the core (2) from the preferably mono-chromatic transmitter (5) that is used as a light source can not leave the core (2) since the refractive index of the cladding (3) that surround the core (2) is lower than the refractive index of the core (2); hence, is reflected from the cladding (3) and is transmitted inside the core (2). During this transmission light travels as it is reflected from the detector (4).
  • Moisture content of the medium is detained due to the hydrophilic material present in the coating material of the detector (4) when the fiber optic sensor (1) is situated in the medium that it is to be used.
  • a hydrophilic material PEG detains too much moisture; hence, although the moisture level of the medium decreases PEG can not release this excessive moisture content.
  • optical sensitivity of the detector (4) of the fiber optic sensor (1) which is bonded as a cross-bond on PMMA and which is affected from hydrophilic material, can not produce a linear output due to this excessive moisture content. For this reason, coating material is prepared with hydrophilic materials and hydrophobic materials.
  • Hydrophobic material avoids the detaining and releasing mechanisms of the moisture content of a hydrophilic material and the accumulation of excess moisture molecules inside the hydrophilic material, and simplifies and organizes the release of water molecules that settle inside the hydrophilic material in the shortest time when moisture concentration decreases, and that has a property of repelling moisture. Therefore, the linearity and repeatability of the output of the detector (4) is established; hence, sensitivity is enhanced.
  • the detector (4) is glued on organic / inorganic surfaces for long periods and a fiber optic sensor (1) with repeatable fiber optic sensor (1) measurement and increased dynamic range and sensing susceptibility is obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Paints Or Removers (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)

Description

  • This invention relates to a coating material that is applied on organic and/or inorganic surfaces and to a fiber optic sensor where this coating material is used.
  • Polyethylene Glycol (PEG) has a very high hydrophilic (likes water) property, detaining moisture. For this reason, its usage is well known especially for moisture sensor applications. However, certain problems are experienced when sensor material particularly Polyethylene Glycol (PEG) is to be coated on surfaces of glass or plastic fiber optic materials. Especially for fiber optic moisture sensors, PEG material that is applied as moisture sensitive sensor material, can not release the moisture content that it has detained at high moisture levels; thus, adversely affecting the repeatability and linearity of the data that the moisture sensor detects.
  • In the current state of art, United States Patent US5109442 describes a fiber optic sensor structure which repels water from its surface and which includes long, hydrophobic (dislikes water) chained polymeric silanes. Polymeric silanes have general structures where alkyltrialkoxysilanes or octadecyltrimethoxysilanes are used.
  • JP2003270141 discloses an optical fiber humidity sensor comprising a mixture formed of a hydrophilic material and a water-insoluble material as cladding layer.
  • The object of the present invention is to realize a fiber optic sensor according to the subject-matter of claim 1.
  • The fiber optic sensor is illustrated in the attached figures, where:
  • Fig. 1 - is a schematic view of a fiber optic sensor.Parts shown in figures are numbered as follows:
    1. 1. Fiber optic sensor
    2. 2. Core
    3. 3. Cladding
    4. 4. Detector
    5. 5. Transmitter
    6. 6. Receiver
  • The fiber optic sensors (1) are particularly affected by moisture level deviations, and sense moisture levels.
  • Coating material that is the object of the present invention comprises a hydrophilic material that has a property to attract moisture that is applied on organic or inorganic surfaces and a hydrophobic material that avoids the detaining and releasing mechanisms of the moisture content with a hydrophilic material that attracts moisture and the accumulation of excessive moisture molecules inside the hydrophilic material, that simplifies and organizes the release of water molecules settled inside the hydrophilic material in the shortest time when moisture concentration decreases, and that has a property of repelling moisture.
  • As hydrophilic material, olygomer and/or polymer materials that are sensitive to various chemicals of hydroxyl, amino, thiol or carboxyl may be used. For the preferred application of the invention polyethylene glycol (PEG) which has a property to detain moisture is utilized as a hydrophilic material.
  • As hydrophobic material; on the other hand, materials that comprise perfluoroalcohol (PFA) group which is known to have a hydrophobic and moisture repelling property are used. For the preferred application of the invention, preferably perfluoroalkyletylalcohol is used as perfluoroalcohol.
  • The coating material comprises a binding agent that increases the grip of the hydrophilic and hydrophobic material to the surface to be coated. The binding agent has an adhering effect and as a binding agent trialcoxy silane group preferably gamma - isocyanatopropyltriethoxysilane is applied.
  • When hydrophilic material is prepared, moisture content of the PEG material is removed with the dean-stark distillation inside toluene solvent methodology. PEG and toluene solution, from which moisture content is removed, is processed with gamma - isocyanatopropyltriethoxysilane as the binding agent with adhesive effect. During this process, hydroxyl (OH) groups with hydroxyl ends in PEG material react with gamma - isocyanatopropyltriethoxysilane, one of the trialcoxy silane groups used as a binding agent, and after this reaction trialcoxy silane groups bind with a urethane bond to the ends of PEG chains. By binding PEG and gamma - isocyanatopropyltriethoxysilane, hydrophilic material and binding agent mix that has an end group of trialcoxy silane is obtained. The general formula of the hydrophilic material, the compound of PEG with trialcoxy silane coated end groups formed after the reaction of PEG and gamma - isocyanatopropyltriethoxysilan is as follows:
  • Figure imgb0001
  • When hydrophobic material is prepared, PFA and gamma - isocyanatopropyltriethoxysilane used as a binding agent are processed with the use of a solvent. The solution is mixed by the addition of a catalyst, tin (II) 2-ethylhexanoate, to the solution obtained at the end of this process. The general formula of the hydrophobic material and the binding agent is given as follows:
  • Figure imgb0002
  • Coating material is obtained by dissolving and/or dispersing the hydrophilic and hydrophobic material and binding agent mixture in water with certain proportions and different concentrations. For example:
  • In one of the preferred applications of the invention, 3.75 mmol PEG material with a hydroxyl end is dissolved in 180 ml toluene solvent. This solution is processed with dean-stark distillation method for 3 hours and moisture content that is trapped inside the PEG material is removed from the material. PEG and toluene solution, with the moisture removed from its content, is processed with 7.5 mmol gamma - isocyanatopropyltriethoxysilane for a certain period at approximately 50 °C; hence, the hydrophilic material and binding agent mixture is obtained. In addition, PFA, particularly 6 g perfluoroalkylethylalcohol, and 3.41 g gamma - isocyanatopropyltriethoxysilane that is used as a binding agent is dissolved in 42 ml tetrahydrofuran solvent. Tin (II) 2-ethylhexanoate is included in this solution as a catalyst and the solution is mixed. At the end of this process PFA reacts with one of the trialcoxy silane groups, gamma - isocyanatopropyltriethoxysilane, which is used as a binding agent and as a result of this reaction trialkoxy silane groups bind with urethane bonds to the ends of PFA chains. By combining PFA and gamma - isocyanatopropyltriethoxysilane, a mixture of hydrophobic material and binding agent is obtained. Additionally, by combining the hydrophilic material, hydrophobic material and binding agent mixture, coating material is obtained.
  • It is possible to coat the material on organic and/or inorganic surfaces such as PMMA materials from which fiber optic sensors (1) are manufactured. Coating material can also be applied on silica glass material.
  • The fiber optic sensor (1) comprises a core (2) that is used as a light transmission line and that is preferably manufactured from plastic fiber optic material, a cladding (3) which thoroughly surrounds the core (2) and has a lower refractive index than the refractive index of the core (2) and is preferably manufactured from a plastic fiber optic material, a detector (4) manufactured from the coating material that is coated on organic or inorganic surfaces , a monochromatic transmitter (5) that is used as a light source and a receiver (6) that senses light.
  • In the fiber optic sensor (1), a core (2) which is preferably manufactured from PMMA material is used. The part of the cladding (3) which thoroughly surrounds the core (2) is partially or completely scratched just up to the surface of the core (2) with various methods; thus, the part that will be coated with the detector (4) is revealed. The detector (4) manufactured from the coating material that includes hydrophilic and hydrophobic material is easily coated permanently to this part that is formed by scratching the cladding (3), creating a cross bond on PMMA material. Detector (4) is coated preferably with dip coating method.
  • Light that is transmitted into the core (2) from the preferably mono-chromatic transmitter (5) that is used as a light source can not leave the core (2) since the refractive index of the cladding (3) that surround the core (2) is lower than the refractive index of the core (2); hence, is reflected from the cladding (3) and is transmitted inside the core (2). During this transmission light travels as it is reflected from the detector (4).
  • Moisture content of the medium is detained due to the hydrophilic material present in the coating material of the detector (4) when the fiber optic sensor (1) is situated in the medium that it is to be used. However, as a hydrophilic material PEG detains too much moisture; hence, although the moisture level of the medium decreases PEG can not release this excessive moisture content. Moreover, optical sensitivity of the detector (4) of the fiber optic sensor (1), which is bonded as a cross-bond on PMMA and which is affected from hydrophilic material, can not produce a linear output due to this excessive moisture content. For this reason, coating material is prepared with hydrophilic materials and hydrophobic materials. Hydrophobic material avoids the detaining and releasing mechanisms of the moisture content of a hydrophilic material and the accumulation of excess moisture molecules inside the hydrophilic material, and simplifies and organizes the release of water molecules that settle inside the hydrophilic material in the shortest time when moisture concentration decreases, and that has a property of repelling moisture. Therefore, the linearity and repeatability of the output of the detector (4) is established; hence, sensitivity is enhanced.
  • When the moisture concentration of the media where the fiber optic sensor (1) is located deviates, optical properties of the detector material; hence, its refractive index deviates which results in the increase or decrease in the amount of light that is transmitted inside the core (2) and the moisture concentration of the media can be computed according to the amount of light that can be transmitted from the core (2) of the fiber optic.
  • By the application of the coating material that is the object of the present invention, the detector (4) is glued on organic / inorganic surfaces for long periods and a fiber optic sensor (1) with repeatable fiber optic sensor (1) measurement and increased dynamic range and sensing susceptibility is obtained.

Claims (6)

  1. A fiber optic sensor (1) that senses moisture level comprising a core (2) that is used as a light transmission line, a cladding (3) which thoroughly surrounds the core (2) and has a lower refractive index than the refractive index of the core (2), a monochromatic (5) transmitter that is used as a light source and a receiver (6) that senses light and a detector (4) that is coated on the part that is generated after the partial or complete scratching of the cladding (3) and that is manufactured from a coating material in the form of a mixture, characterized in that the mixture consists of
    a hydrophilic material that has a property to attract moisture, a hydrophobic material that has a property of repelling moisture and a binding agent that increases the grip of hydrophobic and hydrophilic material on the surface to be coated.
  2. A fiber optic sensor as described in claim 1, wherein the hydrophilic material comprises polyethyleneglycol (PEG).
  3. A fiber optic sensor as described in claim 1, wherein the hydrophobic material comprises a perfluoroalkol (PFA) group.
  4. A fiber optic sensor as described in claim 3, wherein the hydrophobic material comprises perfluoroalkylethylalcohol as PFA.
  5. A fiber optic sensor as described in claim 1, wherein the binding agent comprises trialcoxy silane.
  6. A fiber optic sensor as described in claims 1 and 2, wherein the binding agent comprises gamma - isocyanatopropyltriethoxysilane.
EP05765633A 2004-07-23 2005-07-19 Fiber optic moisture sensor Expired - Lifetime EP1771394B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR200401827 2004-07-23
PCT/IB2005/052397 WO2006011117A2 (en) 2004-07-23 2005-07-19 Coating material and fiber optic sensor in which this coating material is used

Publications (2)

Publication Number Publication Date
EP1771394A2 EP1771394A2 (en) 2007-04-11
EP1771394B1 true EP1771394B1 (en) 2012-09-05

Family

ID=35197873

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05765633A Expired - Lifetime EP1771394B1 (en) 2004-07-23 2005-07-19 Fiber optic moisture sensor

Country Status (5)

Country Link
US (1) US7773835B2 (en)
EP (1) EP1771394B1 (en)
ES (1) ES2393925T3 (en)
TR (1) TR200700301T1 (en)
WO (1) WO2006011117A2 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010000308B4 (en) * 2010-02-04 2012-05-31 Bundesanstalt für Materialforschung und -Prüfung (BAM) Humidity sensor and method for moisture measurement
DE102011080328B4 (en) 2011-08-03 2020-09-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Waveguide and connector
JP6251692B2 (en) * 2012-02-28 2017-12-20 スリーエム イノベイティブ プロパティズ カンパニー Sheeting article with a release coating comprising a polyorganosiloxane and a hydrophilic component
US10712224B2 (en) * 2017-05-19 2020-07-14 The Trustees Of Columbia University In The City Of New York Integrated optical surveillance systems for changes in physical parameters

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894992A (en) 1972-11-24 1975-07-15 Du Pont Fluorinated oily soil release agents
JPS61201143A (en) 1985-03-04 1986-09-05 Agency Of Ind Science & Technol Gas sensor
US5109442A (en) * 1990-03-28 1992-04-28 Fiberchem Inc. Waterproof optical fiber chemical sensor and method of making same
US5119463A (en) * 1991-04-09 1992-06-02 Abbott Laboratories Compound optical probe employing single optical waveguide
JPH0694623A (en) 1992-09-11 1994-04-08 Tdk Corp Humidity sensor
US5326531A (en) 1992-12-11 1994-07-05 Puritan-Bennett Corporation CO2 sensor using a hydrophilic polyurethane matrix and process for manufacturing
EP0606174A1 (en) 1993-01-05 1994-07-13 Elf Atochem S.A. Solid with hydrophobic and oleophobic coating and process for applying such coating
US5403746A (en) * 1993-11-30 1995-04-04 Minnesota Mining And Manufacturing Company Sensor with improved drift stability
EP0875752A1 (en) 1997-05-02 1998-11-04 Yamatake-Honeywell Co. Ltd. Moisture sensitive element and method of manufacturing the same
TW571093B (en) * 1998-12-28 2004-01-11 Tdk Corp Moisture sensor
DE10056771C2 (en) 2000-03-20 2002-08-01 Cis Inst Fuer Mikrosensorik Gg Arrangement for measuring the gas moisture
JP2003270141A (en) 2002-03-15 2003-09-25 Shinzo Muto Optical fiber humidity sensor and humidity detection system and respiration detection system using the same
US7119137B2 (en) * 2003-09-18 2006-10-10 Amcol International Corporation Moisture-impervious water-swellable clay-containing “water-stop” composition

Also Published As

Publication number Publication date
TR200700301T1 (en) 2007-04-24
ES2393925T3 (en) 2013-01-02
WO2006011117A3 (en) 2006-04-20
US7773835B2 (en) 2010-08-10
US20080240667A1 (en) 2008-10-02
EP1771394A2 (en) 2007-04-11
WO2006011117A2 (en) 2006-02-02

Similar Documents

Publication Publication Date Title
US8772373B2 (en) Coating composition, coating and an object coated with the coating composition
US7864321B2 (en) Evanescent wave multimode optical waveguide sensor with continuous redistribution of optical power between the modes
Jin et al. Polymer fiber optic sensors-a mini review of their synthesis and applications
US20110085759A1 (en) Composite thin film, and atmosphere sensor and optical waveguide sensor each including the same
Chen et al. EDC-mediated oligonucleotide immobilization on a long period grating optical biosensor
JPH0772082A (en) Chemically Sensitive Fiber Optic Cable
CA2110533A1 (en) Co2 sensor using a hydrophilic polyurethane matrix
EP0274184A1 (en) Dye silane compositions
US7773835B2 (en) Coating material and fiber optic sensor in which this coating material is used
US6139799A (en) Membranes and optical sensors made therewith having improved barrier properties
Santano et al. Regenerable LMR-based fiber optic immunosensor with a SnO2 metallic oxide thin film for label-free detection
Zahra et al. Advanced novel asymmetric notched plastic optic fibers for sensing applications
Eaton et al. In situ and ex situ FTIR–ATR and Raman microscopic studies of organosilane hydrolysis and the effect of hydrolysis on silane diffusion through a polymeric film
WO2005090253A2 (en) Coating material and a fiber optic sensor in which this coating material is used
CA2590813C (en) Evanescent wave multimode optical waveguide and sensor with high mode coupling
Chen et al. PDMS-based optical leaky waveguide coated with self-assemble Au-NPs for bio-analytical detections
JP2005221297A (en) Optical fiber sensor
WO1992015862A1 (en) A waveguide sensor
JP7608103B2 (en) Fiber optic articles, their manufacture and use
Corres et al. Experimental results of antigliadin antibodies detection using long period fiber grating
Butler Development of evanescent wave pH sensors based on coated optical fibres
Novak et al. Analysis of the bending radius of the cylindrical waveguide of polydimethylsiloxane for the purpose of lighting
Azargoshasb et al. Controllable in Situ Fabrication of Versatile Polydopamine-Based Lossy Mode Resonance Functionalized Optical Fiber Towards the Epinephrine Recognition and Detection
JP2008195553A (en) Anti-fogging glass substrate for cutting multiple sheets therefrom
JP2010071691A (en) Body fluid inspecting and measuring instrument and cover member

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070125

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20070522

DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602005036009

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C03C0025000000

Ipc: G01N0021770000

RIC1 Information provided on ipc code assigned before grant

Ipc: C03C 25/10 20060101ALI20111128BHEP

Ipc: C09D 175/04 20060101ALI20111128BHEP

Ipc: C08G 18/71 20060101ALI20111128BHEP

Ipc: C03C 25/16 20060101ALI20111128BHEP

Ipc: C08G 18/28 20060101ALI20111128BHEP

Ipc: C03C 25/68 20060101ALI20111128BHEP

Ipc: C08G 18/48 20060101ALI20111128BHEP

Ipc: G01N 21/77 20060101AFI20111128BHEP

RTI1 Title (correction)

Free format text: FIBER OPTIC MOISTURE SENSOR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 574328

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120915

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602005036009

Country of ref document: DE

Effective date: 20121031

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2393925

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20130102

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 574328

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120905

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120905

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

Effective date: 20120905

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121206

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130105

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130107

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121205

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

26N No opposition filed

Effective date: 20130606

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602005036009

Country of ref document: DE

Effective date: 20130606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120905

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130719

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20050719

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20160621

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20160721

Year of fee payment: 12

Ref country code: IT

Payment date: 20160725

Year of fee payment: 12

Ref country code: DE

Payment date: 20160722

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20160721

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20160715

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602005036009

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170719

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20180330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180201

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170719

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20181105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170720

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170719